Unsaturated epoxides and method for making same



3,203,939 UNSATURATED EPOXIDES AND METHOD FOR MAKING SAME Samuel W. Tinsley, Jr., and Edward A. Rich, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York 'No Drawing. Filed Feb. 8, 1962, Ser. No. 171,814

"18 Claims. (Cl. 26048.1)

This invention relates to a novel process for preparing unsaturated epoxides, and to the unsaturated epoxides obtained thereby. In particular, this invention relates to organic compounds containing a polymerizable unsaturated group, e.g., a vinyl group, and an epoxy group comprising oxygen bonded to two vicinal carbon atoms. In various other aspects the invention relates to novel polymers obtained by polymerizing the novel unsaturated epoxides of this invention through the polymerizable unsaturated groups thereof and/or through the epoxy groups thereof.

' The polymerizable unsaturated epoxides made by this invention are well suited for use in resin-forming operations, such as coating, laminating, bonding, molding, casting, potting, and the like. They are self-polymerizable and also co-polymerizable with Various other organic materials such as other polymerizable unsaturated organic compounds, other epoxides, and the well-known active organic hardeners, e.g., polycarboxylic acids (including the polycarboxy polyesters), polycarboxylic acid anhydrides, polyols, polythiols, polyisocyanates, polyacyl halides, and the like. Compositions containing the com- 7 pounds produced by this invention, with or without copolymerizable materials as set forth above and/ or special additives for producing special effects, are compatible with solid materials such as fillers and pigments for providing various effects in physical properties and coloration.

- With or without such added solid materials, these polymerizable compositionscan be made to fill small intricacies of molds without the necessity of applying high pressures and heating to high temperatures, although such measures can be employed if desired. The polymerizable compositions also can be easily spread, brushed, or sprayed by manytechniques available in the point, lacquer, and varnish industries for making-coatings and finishes. Negligible shrinkage, if any, occurs in curing to the resin. The polymerizable compositions are capable of being accuratcly shaped by molds having intricate molding surfaces and-fully cured to resins carrying exact details of such molding surfaces. They can be also advantageously employed in the potting of such fragile articles as electronic components.

The polymerizable compositions described above also can be. partially reacted at elevated temperatures to form viscous thermosetting liquids or thermosetting solids. The resulting fusible thermosetting intermediate reaction products can be dissolved in an inert normally-liquid organic medium and applied as heat-curable coatings. To aid solu tion, the thermosetting solid products can be powdered or granulated, if desired. The thermosetting solids also can be used as molding powder compositions which can be converted to fully cured solid products by the application of heat and/ or pressure. Numerous other uses, applications, and unexpected advantages and results will become *United States Patent 3,203,939 Patented Aug. 31, 1965 "ice ' epoxyalkyl ethers or vinyl vic-epoxyalicyclic ethers. The

term vie-epoxy, as employed herein, refers to' an oxirane oxygen connected to vicinal carbon atoms, e.g.,

The term vic-epoxyalicyclic, as employed herein, includes vic-epoxymonocycloalkyls, e.g., 2,3-epoxycyclopentyl, and vic-epoxypolycycloalkyls, e.g., 4-oxatetracyclo[6.2.l.O .0 ]undec-9(l0) yl, and alkyl-substituted I and aryl-substituted derivatives thereof. Any suitable temapparent upon a consideration of the various embodiments of the invention which are discussed hereinafter.

The novel process of this invention comprises the etherification of a vic-epoxyalkanol or a vic-epoxyalicyclic alcohol with a vinyl ether or a vinyl ester wherein the vicepoxy group is connected through at least one carbon atom to the alcoholic hydrnxyl group in the presence of the mercuric salt of a weak ncid, preferably a mercuric alkanoatc. it has been unexpectedly found that such an etherification in the presence of the mercuric salt of a peratures which will effect the etherification can be employed. Illustrative temperatures generally lie in the range of 25? C., and lower, to C., and higher.

The etherification reaction involved in the novel process is reversible. Once equilibrium has been established, the catalyst is destroyed, and the desired vinyl vie-epoxyalkyl ether'or vie-epoxyalicyclic ether is separated and recovered by suitable means, such as fractional distillation. It is particularly advantageous, however, to force the reaction I to completion by continuously removing the desired vinyl vie-epoxyalkyl ether or vie-epoxyalicyclic ether from the reaction mixture. This can frequently be accomplished by selectively distilling the vinyl vie-epoxyalkyl ether-or vic-epoxyalicyclic ether from the reaction mixture, since these, in general, boil at a sufiiciently lower temperature than the corresponding alcohols from which they are derived.

While mercuric acetate is the preferred catalyst, other Y mercuric salts of weak acids can be employed. Suitable catalysts illustratively include mercuric oxalate, mercuric citrate, mercuric linoleate, mercuric propionate, mercuric butyrate, mercuric chromate, and the like. Mercuric alkanoates are particularly effective as catalysts for these etherifications. Mercuric salts of strong acids are suitable catalysts only when they do not preferentially catalyze the formation of acetals or catalyze the decomposition of the vic-epoxide. 1 v

Vinyl ethers and vinyl esters which can be employed as reactants (vinylating agents) in the etherification process of this invention are any of the vinyl organic ethers and vinyl organic esters which do not otherwise react with I 1,2-epoxy groups or alcoholic hydroxyl groups, such as those in the vic-epoxyalkanol or the vic-epoxyalicyclic alcohol reactants, under the conditions of said process. The

preferred vinylating agents are the vinyl alkyl ethers, such as vinyl n-butyl ether, vinyl 2-ethylhexyl ether, vinyl n-octyl ether, vinyl 2-butoxyethyl ether, and the like, and

the vinyl alkanoates, such as, vinyl acetate, vinyl butyrate, vinyl hexanoate, and the like.

The vic-epoxyalkanols and the vic-epoxyalicyclie alcohols employed as reactants in this process include glycidol, 2,3 epoxycyclopentanol, 4-oxatetracyclo[611.0 .0 1 undecan-9(or 10)-ol, 2,3-epoxybutanol, 2-methy1-2,3-epoxypropanol, Z-methyl-Z,3-epoxybutanol, 2,3-epoxypentanol, 2,3-epoxyhexanol, 2,3-epoxyoctanol, 10,l1-epoxyundecanol, 9,10-epoxydecanol, 9,10-epoxyoctadecanol, 4- methyl-2,3-epoxycyclopentanol, 4-isopropyl-2,3-epoxycyclopentanol, 3,4-epoxycyclohexanol, 3-ethyl-3,4-epoxycyclohexanol, 4-methyl-2,3-epoxycyclohexanol, 6-n-butyl- 3,4-epoxycyclohexanol, S-amyl 3,4- epoxycyclohexanol, 2,4-diethyl-3,4 epoxycyclohexanol, 3,4epoxycycloheptanol, 2,3-epoxycycloheptanol, 2,3-epoxycyclohexanol, 2,3- epoxycyclooetanol, 2,3-epoxycyclopentylmethanol, 3,4-

- epoxycyclohexylmethanol, 2-n-propyl-3,4-epoxycyclohexsubstituted 4 oxatetracyclo[6.2.l.o -htl jundecan-ymr I ll D-ol, and the like.v

3 Asemployed herein, the term lower alkyl designates an alkyl group having'from l to 4 carbon atoms.

The vic-epoxyalkanolsI-and the vic-epoxyalicyclicr alcohols are, for the most part; known in the prior art. However, they can be'prepared' by reactingtthe.corresponding alkenols and olefinically unsaturated alicyclic alcohols,

e.g.,- monoandpolycycloalkenols, with an aliphatic peracid, such'as'peracetic acid, as a. 10 to '50 weight percent solution inan inert organic solvent at a temperature in theqrange of about C., or lower, to about 100 C. The amount of peracetic acidemployed. should be at least one mole per mole of thercarbon :to carbon double. bond of the'alkenol or'monoor polycycloalkenol and. preferably should be '10 to 25xpercentsgreater and the-reaction 3-en-8(or9)-'ol, the percursor for 4-oxatetracyclo[6.2.l.-

0"" .0 ]undecan-9(or 10)-ol,.is effected by reactingdi- .time should bessuiiicient to introduce oxiraneoxygen at the site'ofeachrarbon' to carbon double bond desired to be epoxidized. The preparation of tricyclo[5'.2.1.0 ]deccyclopentadiene-withan aqueous solutionof'an inorganic acidie 'catalyst; e.g., an aqueous solutionof weight percent sulfuric acidat an'elevated temperature, e.g., fromabout.75' C., or lower, to about125 C., and higher;

The novel unsaturated epoxides of this invention-are the vinyl vic-epoxyalicyclie ethers, composed of 'carbona'hydrogen' and'oxygenewherein said oxygenisin'the-form of etheric'oxygen and. oxirane 'oxygen and wherein the car- 'formula- CH,=CH=OR-, wherein R represents a vicepoxyalicycliegroup; More specifically, -.R is (1) a vie? epoxycycloalkyl group, preferably containing-5 to: 8 carbon atoms, .wherein'the vie-epoxy group" is contained in the cycloalk'yl ringand isconnected'to theethercoxygen of the aboveformula'throughiat least one carbon atom;

(2)1a'vie epoxycycloalkflalkyl group having a vie-epoxy cycloalkyl' groupas describedabove; (3) a.3-oxatricyclobon'atoms of thevic-epoxy group arein the alicyclic ring.

The novel vinyl vie-epoxy ethers: are represented by the oct-6-ylalkyl group; (5) a 4-'oxatetracyclo [6:2;10 -10 0 .0 ]undec-9(or 10)-ylalkyl group; Specific illustrations of-R include. 2,3-epoxycyclopenty], 4-methyl -2;3--

epoxycyclopentyl, 4-isopropyl-2',3-epoxyeyclopentyl, 3,4 epoxycyclohexyl, 3-ethyl-3;4-epoxycyclohexyl, 4 rnethyl- 2,-3-epoxycyclohexyl, 6-n-butyl-3,4-epoxycyclohexyl, 5- amyl-3,4-epoxycyclohexyl, 2,4-diethyl-3,4-epoxycyclohexyl, I 3,4epoxycycloheptyl, 2,3epoxycycloheptyl, 2eethyl- 3,4-epoxycycloheptyl,

clohexylamyl, 2,3 epoxycycloheptylmethyl, 3=oxatricyclo- 9(01' I0)yl,.lower alkyl substituted 4-oxatetracyclo'[6.2.

1.0 9 undec-9(or 10)'-yl,' and:.the like.

The novel compounds I produced: by this' invention in clude vinyl 2,3-epoxycyclopentyl ether, vinyl 4-methyl-2',3-- "epoxycyclopentyl ether, vinyl '4-isopropyl 2;3 epoxycyclopentyl ether, vinyl 3,4-epoxycyclohexyl ether; vinyl'3-ethyl 3,4-epoxycyclohexyl ether, vinyl -4-methyl-2,3 epoxycyclo= hexyl ether, vinyl 6-n-butyl'-3,4-epoxycyclohexyl ethergvin 'yl 5-amyl-3,4 epoxycyclohexyl ether, vinyl"2,4-diethyl-3,-4'-- epoxycyclohexylether, vinyl 3,4-epoxycycloheptyl ether,

vinyl 2,3-epoxycyclohcptylether, vinyl 2-ethyl-3j4-epoxy cycloheptyl ether; vinyl 2,3-epoxycyclopentylmethy'l ether, vinyl 3,4-epoxycyclohexylmethyl ether, =vinyl Z-n-pr'opyl- :3,4-epoxycyclohexylmethylether; vinyl S-ethyl-BA-epoxycyclohexylpropyl ether, vinyl 3,4epoxycyclohexylamyl 2,3.-epoxycyclopentylmethyl, 3,4 epoxycyclohexylmethyl, 2-n -:propyl-3,4-epoxycyclohexylmethyl, 5-ethyl-3',4-epoxycyclohexylpropyl, 3;4-epoxycy-- The novel unsaturated epoxidcs of thistinvcntion can bev self-polymerized through the vinyl .groupthereof or covpolymerizcd. through the vinyl group. thereof with other polymerizable olefinicallysunsaturated .organicmon omers 'to produce novel polymers: which containqgroups having;the formula. v

wherein R isas prcviously defined, with or without groups derivablevfrom the polymerizableolefinically unsaturated compound, e.g., havingthe formula R. 11' ALL. A! if wherein R can-be the same or-different groups selected fromthe class consisting ofhydrogen; alkyl, aryl; and

the like. These polymers arev obtained by employing vinyl polymerizationcatalysts such asbenzoyl peroxide,

t-butyl hydroperoxide; cumenerhydroperoxide, acetyl peroxide, p-menthane hydro'peroxide, lauroyl peroxidefdi-t butyl peroxide,. t-butylv perbenzoate, and; the. like. Illustrativepolymerizable 'olefi'nically, unsaturated monomers include. the, heptenes, .nonenes',i ethylene, propylene, isobutylene, hexadiene, cyclopentene, cyclohexenes, styrene, divinylbenzene, divinyl ether; diallyl ether, methyl mcthacrylate, methyl acrylate,.ethylacrylate,maleic.anhydride; maleicvanhydride polyesters, acrylic acid,vvinyl chloride; vinyl. acetate, and: the like;

groups or vic-.epoxypolycycloalkoxy groups, i.e., or

groups, g

In addition, the novel unsaturated"; epoxides'of this inventiorrcan beself-polymerized. through-their vic-epoxy groups. or coepolymerized...throughz their viceepoxyz groups with other vicsepoxy organic compounds, such as ethylene:

oxide,-propylene..oxide, dicyclopentadiene dioxide, divin'ylhenzenedioxide, vinylcyclohexene dioxide; butyleneoxide, cyclohexene oxide; and: the. like. The -polymerizations or co-poly'merizations through ,thevic-epoxy'igroups is best.v conductediinithe. presence oflbasic catalysts at such' temperatures-asiab'out.25"'C; to about 250 C. Illustrations of'suitable basic; catalysts. include the. alkali';metal. hy-

droxides, organicsamines, e.g. triethylamine;-.and thei like.

' In addition, the: novel unsaturatedyepoxides: of "this in-- v'entioncan be: polymerized through the.-wvic-.epoxy rgroup with" activeorganic hardeners, such as polycarboxylic:

acids, 'polycarboxy polyesters, polycarboxyliciacidianhydrides, polyols, e.gr, polyhydric; phenols, polyhydric; aicoi hols, and .polyhydric polyesters;. polyfnnctional .arnincs, polythiols, polyisocyanates, polyisothiocyanates,'polyacyl halides, and the. like,'-..by mixing: said. epoxides:-,withsaid hardener and maintaining the resulting-mixtureatatemv peraturefrom about: 2S'C.".to 25.0""CL flt-hervic-epoxy organic compounds," as: set forth-above, can. lbc addedstothe mixture; of the novel vicinalaunsaturated: epoxidigs :and

organic. hardener asdesired; Basic catalysts; as described.

above; can. also be employedto.increase'the rate oftpolym 'erization' or' decrease; the polymerization.:temperaturc:

Polymerstand/ or co-polymers obtained? by" polymeriz-- ing the novel unsaturated epoxidcs, through thevic-epdxy group thereof, withor without other vicinal-epoxy com.- pounds: andwith or withoutorganic hardeners contain: groups otthe formula 1 (iIII=C H Such polymers comprisepa. chainrof carbonc'atomsand pendanti-viceepoxycycloalkoxy 55 wherein R' is a trivalent saturated aliphatic hydrocarbon group or a trivalent saturated. cycloaliphatic hydrocarbon group and wherein each R" is a hydrogen. or alkyl and wherein the novel unsaturated. epoxide of this invention is represented bytheformula.

wherein R and'R' are as defined above;

Preferably, R" in each of thev above-formulas is a. tr'u.

, ,valent: alkane or: alicyclic group having?! 'tof6 carbon atoms. in a chain connecting. the:-R"-bondedv carbon: atoms, e.g.,

tit-er! an bro-ch, l

Representative;- active organic :hardeners for-admixture and/or reaction. with the novel unsaturated epoxides. ",clude oxalic acid, succinic. acid; glutaricacid, adlPlQaFld, suberic. acid, alkylsuccinic acids, alkenylsuccimc acids,

maleic. acid, iitaconic. acid, allylmal'onic acid, -3-hexynedioic acid, 1,-2.-cyclohexanedicarboxylicn acid;.. phthalie acid, terephthalic: acid, 'phthalic: anhydride, tetrahydro phthalic' anhydn'de, maleic anhydride, glutan'c anhy dride, succinic anhyd'ride, nonenylsuccinic anhydride',

1,8-naphthalic: anhydride, lower" alkyl' substitutedebi' cyclo[-2.2.l]hept'- 5' ene- 2,3. dicarboxylic1 anhydride,

methylbicyclolZl.llhept -2 ene 2,3T dicarboxylic anhydride, ethylene: glycol, diethylene glycol, the polyglycols, 1,1,1-trimethylo1propane,the polyvinyl alcohols, the 'cyclopentanediols', the: cyclohexanedi'ols, resorcinol;

catechol, bis(4-hydroxyphenyl)-2,2-propane, l,8-naphtha'-- lenediol, polycarboxypolyesters 'preparedt'by known condensation' procedures, employing mol ratios favoring- I ethylene glycols, propylene glycol; the' polypropylene greater than; equivalent amounts ofi polycarboxylicacid I or polycarboxylic acid anhydride, such as. those listed;

above, withrelation to" the polyhydric' alcohol; such. as."

those listed. above, and: polyhydroxy polyesters preparedby procedures, employing. mol; ratios. flavoring; greater than equivalent amounts of poliyhydric: alcohol '1 with relation: to: the polycarboxylic': acid orzanhydride... I

The following. examples-are illustrative? EXAMPL-Hal Vinyl n-butyl ether (300 g.),-.4-oxatetracyclo[6:2;1.0 .0 ]undec a.ne-9(or' 10)-ol-:-( 8 2i g.)} and mercuric acetate 1 (2.5 g'.) werecharged to a one'literiflaslr, andztheiresultant? p solution. was refluxed at atmospheric pressure fonsix :hours; The catalyst was then destroyed'byrthe. addition of .an'hydrous potassium carbonate (5 g'.),. and the volatiles were: removed. under reduced; pressure; The: residue: wasv 5 iractionated atreduced pressurelto. yield'the product'(2 9.7 yield. based on: chargeda. 4-oxatotracyclo- The vinyl 9(l0)-4,-' oxatetracyclo[61*2.1.0 ";0 ]undecyl): ether: thus:;obta ined I g.:: 31% [6.2.1.0 ".0 ]undecane-9(l0) ol).

had the-following physical; properties: BLP: 106A 14' C.-/3

mm; n 3WD 15070-15079; Arhear-ts :cut (\B,.P.. 1 121 i ide determination (hydrogen-bromide-method); The in-.- frared spectrumwas consistentwith theassignedastrueture;

Elemental analysis provided; the following results;

EXAMPLE. 2

I Viriyl 2,3 ep0xycyclo1rentylether A): Vinyl n-butyl ether: (160.0 g); 2,3.-epoxycycloperitanola (400 g.),: and: mercuric. acetate (-24 g.): werei-chargedi.

to a five-liter'flask, andthe:resultant'soluti-onzwas:refluxedi I i at. atmospheric pressurev for: six'hou-rsz. The catalystiwasthemdestroyed by addition-of anhydrous. potassium: carbonate g.),v andlthe reaction mixture was. fractionated undenreduced. pressure; Sixty "four. grams oftl're: desireda product,:.vinyl 2,3-epoxycyclopentyl. ether;:-(B3P5r 7 11 C1510? ram-.45 C./ 18; mm) wasacollectedbeforez the: otiresidue polymerized. The infrared andLr'nassz-speotra; ofjaheartsw cut (BLPZ'7'1' C./ 10 mm'.;, It 3.0/D "-1".4658') were'consistnt' with the proposed structure; Elemental ,analysisprovided the:followingzresultsizv 4 45- C, 66.87%; H; 8.27%.;

found: Q

(B). Vinyl: n-butylIether' (1800 g.),. 2,3'-epoxycycl op en tianol(300 g'.); and mercuric acetater("15.- g'.).:were'ch'arged.fto a v fivedit'er flask, and. thexresultant: solution was; refluxed at atmospheric pressure. fOl'I'SiXi hours; The catalystv was then: destroyed by the: addition or anhydrous" potassium carbon-ate. (301' g.).'. Distillationyieldedta crude product (282 g.).-boilingat.47 C.Z.65i'mm.-33" Cilfl'dmm. This was dissolvedv in benzene" (200 ml.)'*,' washed with: water.

(5-50; portions). toremove: .unreactedalcohohi andi dried over'anhydroussodium sulfate; Redistillationgave therproduct.(-71'.3 g 19% yieldi:basedbonzzcharged,..2,3=ai- 98.2% pure: by epoxid'ezdeterminatiom.(hydrogen 'bromidei method).

. EXAMPLES;

' Vinyl Zlf-epoxypropyfetiier Glycidol- 31.9: g..), vinyl -2+ethylhexyli ether: at

flask. fitted with: am.efiicientrfractionatinga columngi; The mixture: was refluxed: under' reduced pressure: 116 mm.)

and. the lowboiling-product was; taken of slowly; atgthe' L andrnercuric acetate (22;v g. were: chargedrtor-au tw liter.

head. After. a short period offtimerthei two.:phase: reaction-1 mixture; became: homogeneousa.

The Merc -overhead product (221 g.) thus; obtainedtwas. dissolved?inebenzene v;. (500 mm, washediwithzwater'. (-5. 75: ml'i. portions.) -to-rc*. moveunreacte'd" glycidolg, and:v dried; QVeESZll'lhydl'OUS' -SQfliie';

um sulfate. Redistillation yielded vinyl 2,3-epoxypropyl ether (164 g.; 38% yield) having the following properties:

B.P. 38.5 C./15.5 mm.; n 30/D 1.4300-1.4310. A hearts cut (8.1. 38.5 C./15.5 mm.; n 30/D 1.4301) analyzed 93% pure by epoxide determination (pyridinehydrochloride method).

The infrared and mass spectra of vinyl 2,3-epoxypropyl ether, prepared as above, were consistent with the proposed structure. The mass spectrum indicated that the material contained trace to slight amounts of unidentified impurities. Elemental analysis provided thefollowing results:

Calcd. for C l-I C, 59.98%; H, 8.05%. Found: C, 60.47%; H, 8.20%.

EXAMPLE V 4 Vinyl 3-0xatricycla[3.2.1 .0 ]oct-6-yl ether Example 1 isfollowed with the exception that in place of 4-oxatetracyclo[6.2.1.0 .0 ]undecane-9(10)-ol an equal molar amount of 3-oxatricyclo[3.2.l.0 ]octan-6-ol is employed. The resulting product is vinyl 3-oxatricyclo [3.2.1.0- ]oct-6-yl ether.

EXAMPLE 5 Vinyl 5 -oxapentacyclo[7.2.1 .I ..0 "'.0 -]tridecl0-ylmethyl ether Example 2(A) is conducted with the exception'that in place of 2,3-epoxycyclopentanol an equal molar amount of 5 oxapentacyclo[7.2.lA 0 ]tridec-lO-ylmethanol is employed. The resulting product is vinyl S-oxapentacyclo-[7.2.1. l .0 .0 ]tridec-lO-ylmethyl ether.

EXAMPLE 6 I Vinyl 3,4-epoxycyclohexyl ether 7 Example 2(A) is conducted with the exception that in place of 2,3-epoxycyclopentanol an equal molar amount of 3,4-epoxycyclohexanol is employed. The resulting product is vinyl 3,4-epoxycyclohexyl ether.

' EXAMPLE 7 Vinyl 3-0xatricyclo[3.2.1.0 ]oct-6-ylmethyl ether Example 2(A) is followed with the exception that in place of 2,3-epoxycyclopentanol an equal molar amount of 3-ox'atricyclo[3.2.1.0 ]oct-6 ylmethanol is employed. The resulting product is vinyl 3-oxatricyclo[3.2.1.0 ]oct- 6-ylmethyl ether.

EXAMPLE 8 One mole .of ethylene and one mole of vinyl 2,3-epoxycyclopentyl ether are mixed with a, catalytic amount of benzoyl peroxide and heated to approximately 70 C. There is obtained a polymer having pendant 2,3-epoxycyclopentoxy groups.

EXAMPLE 9 One mole of vinyl 2,3-epoxypropyl ether and one mole of ethylene oxide are mixed with a catalytic amount of dibutyl zinc and heated. There results a polymer having vinyl unsaturation.

EXAMPLE 10 One mole of vinyl 3,4-epoxycyclohexyl ether and one mole of succinic acid are mixed and heated. There results a polymer having vinyl unsaturation.

EXAMPLE 11 One mole of vinyl 3-oxatricyclo[3.2.1.0- ]0ct-6-yl ether is mixed with a catalytic amount of dibutyl zinc and heated. There results a polymer having vinyl unsaturation.

EXAMPLE 12 One mole of vinyl 5-oxapentacycloi7.2.l.1 .0 .0 1- tridec-lO-ylmethyl ether is mixed with one mole of 8 phthalic anhydride and the mixture is heated. There results a polymer having vinyl unsaturation.

EXAMPLE 13 One mole of vinyl 3-oxatricyclo[3.2.1.0- ]oct-6-ylmethyl ether is mixed with one mole of ethylene glycol and a catalytic amount of dibutyl zinc and the mixture is heated. There results a polymer having vinyl unsaturation.

' EXAMPLE 14 One mole of vinyl 2,3-epoxycyclopentyl ether, one mole of ethylene diamine, one mole of styrene and a catalytic amount of di-t-butyl peroxide are mixed and theresulting mixture is heated. There results a solid polymer having groups of the formula:

EXAMPLE 15 Vinyl acetate (340 grams), mercuric acetate (3 grams) and sulfuric acid (.05 gram) were placed in a flask and cooled to --20 C. 4-oxatetracyclo[6.2.l.0-".0 -]undecan-9(l0)-ol (166 grams) was then added dropwise over a period of one hour during which the temperature was maintained at 10 to -20 C. Sodium carbonate (63.6 grams) was then added to destroy the catalyst. The resultant mixture was filtered and the filtrate distilled. There was thus obtained vinyl 9(10)-(4-oxatetracyclo- [6.2.1.0' ".0 ]undecyl) ether (16 grams).

. Reasonable variations and modifications of the inven- I tion can be made or carried out in the light of the above disclosure without departing from the spirit and scope thereof.

What is claimed is:

1. Vinyl 3-oxatricyclo[3.2.l.OfiJoct-ti-yl ether.

2. Vinyl 3-oxatricyclo[3.2.l.0" ]oct-6-ylalkyl ether.

wherein R is a trivalent saturated hydrocarbon group which together with the R-bonded carbon atoms forms a member of the group consisting of saturated monocyclic and polycyclic rings, and wherein R" is selected from the group consisting of hydrogen and alkyl.

6. Vinyl vic-epoxycycloalkyl ethers of the formula:

. wherein R is a trivalent saturated hydrocarbon group containing 3 to 8 carbon atoms which together with the R'.'-bonded carbon atoms forms a member of the group 7 consisting of saturated monocyclic and polycyclic rings,

and wherein R" is selected from the group consisting of hydrogen and alkyl.

7. A homopolymer containing pendant unreacted epoxy groups containing repeating units of the formula:

.monocyclic and polycyclic rings, and wherein each R" is individually selected from the group consisting of hydrogen and alkyl.

8. A homopolymer containing pendant unreacted epoxy groups containing repeating units of the formula:

CHa-CH wherein R is a trivalent saturated hydrocarbyl radical containing from 3 to 8v carbon atoms, which together with the two hydrogen-bonded carbon atoms form a member of the group consisting of saturated monocyclic or polycyclic rings. a

9. A homopolymer having pendant vinyl groups con- 10. A homopolymer having pendant vinyl groups con taining repeating units of the formula:

wherein R is a trivalent saturated hydrocarbon group containing 3 to 8 carbon atoms which togethe: with the R-bonded carbon atoms forms a member of;the group consisting of saturated monocyclic and polycyclic rings,

finically unsaturated monomer is ethylene.

and wherein R" is selected from the group consisting of hydrogen and alkyl. I h

11. A solid homopolymer having repeating units of the formula:

OHz-CII 1% R" I wherein R is a trivalent saturated hydrocarbon group which together with the R"-bonded carbon atomsforms a member of the group consisting of saturated monocyclic and polycyclic rings, and wherein R' is selected from the group consisting of hydrogen and alkyl.

12. A copolymer having pendant vinyl groups obtained by copolymerizing through the epoxy groups a member se-. lected from the group consisting of vinyl vic-epo'xymonocycloalkyl ethers and vinyl vic-epoxypolycycloalkyl ethers wherein said monocycloalkyl and polycycloalkyl portions contain from 3 to 8 carbon atoms and a. vicinal epoxy hydrocarbon.

13. The copolymer of claim 12' wherein the vicinal epoxy hydrocarbon is ethylene oxide.

14. A thermosetting solid copolymer obtained by crosslinking the copolymer of claim 12 through the vinyl groups. I

. 15. A copolymer having pendant epoxy groups obtained by copolymerizing through the vinyl groups, a member selected from the group consisting of vinyl vicepoxymonocycloalkyl ethers and vinyl vic-epoxypolycycloalkyl ethers wherein said monocycloalkyl and polycycloalkyl' portions contain from 3 to '8 carbon atoms, and an olefinically unsaturated polymerizable monomer.

16. The copolymer of claim 11 wherein the said ole- 17. The copolymer of claim 11 wherein the said ole finically unsaturated monomer is styrene. i

18. A thermosetting copoplymer obtained by crosslinking the copolymer of claim 15 through the epoxy groups.

References Cited by the Examiner UNITED STATES PATENTS 12/ 5 4 Crecelius 260-348 2,760,990 8/56 Watanabe et al. 260---614 2,847,478 8/58 Hwa et al. 260-611 2,889,339 6/59 Levy et al. 260-348 3,014,048 12/61 Tinsley et al. 260-348 3,065,213 11/62 Vandenberg 260-883 JOSEPH L. SCHOFER, Primary Examiner. 7

WILLIAM H. SHORT, Examiner. 

5. VINYL VIC-EPOXYCYCLOALKYL ETHERS OF THE FORMULA:
 9. A HOMOPOLYMER HAVING PENDANT VINYL GROUPS CONTAINING REPEATING UNITS OF THE FORMULA 